EP3106221A1 - Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen - Google Patents

Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen Download PDF

Info

Publication number
EP3106221A1
EP3106221A1 EP15172157.8A EP15172157A EP3106221A1 EP 3106221 A1 EP3106221 A1 EP 3106221A1 EP 15172157 A EP15172157 A EP 15172157A EP 3106221 A1 EP3106221 A1 EP 3106221A1
Authority
EP
European Patent Office
Prior art keywords
iii
catalyst
process according
equal
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15172157.8A
Other languages
English (en)
French (fr)
Inventor
Gerrit Albert Luinstra
Benjamin Nörnberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universitaet Hamburg
Original Assignee
Universitaet Hamburg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universitaet Hamburg filed Critical Universitaet Hamburg
Priority to EP15172157.8A priority Critical patent/EP3106221A1/de
Priority to PCT/EP2016/063714 priority patent/WO2016202838A1/en
Priority to US15/736,727 priority patent/US20180179334A1/en
Priority to EP16732991.1A priority patent/EP3307432A1/de
Publication of EP3106221A1 publication Critical patent/EP3106221A1/de
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B01J31/0238—Amines with a primary amino group

Definitions

  • the present invention relates to a process for the preparation of a double metal cyanide (DMC) catalyst, to a double metal cyanide catalyst per se, and to its use in polymerization processes, such as a process for the polymerization of alkylene oxides.
  • DMC double metal cyanide
  • Polyether polyols (poly(alkylene oxide) polymers) are widely used, such as in the production of detergents, superplasticizers and polyurethanes.
  • Double metal cyanide (DMC) complexes represent a rather recent class of catalysts suitable for the production of polyether polyols.
  • polyether polyols prepared with DMC catalysts are characterized by a rather low unsaturation level and a rather narrow molecular weight distribution. Both properties are required for the production of high quality polyurethanes.
  • DMC catalysts represent a useful class of catalysts.
  • DMC catalysts for the homopolymerization of alkylene oxides, like propylene oxide and ethylene oxide, their use in the copolymerization of alkylene oxides with CO 2 to yield polyether carbonate polyols ( US 4,500,704 , WO 2013/010986 , WO 2013/011015 , WO 2012/136657 , and WO 2012/136658 ) and in the terpolymerization of alkylene oxides, CO 2 and cyclic anhydrides to yield polyether-ester-carbonate polyols ( WO 2013/087582 ) is known. Therefore, DMC catalysts allow the modification of material properties by selective incorporation of co-monomers. For example, biodegradability can be imparted to the polymer in this way.
  • the polymerization reaction mixture typically comprises a DMC catalyst, one or more monomers and optionally a so-called starter substance.
  • the starter substance can be selected from the group consisting of mono or polyfunctional alcohols, amines or other H-functional compounds. By controlling the ratio of monomer(s) to starter substance(s) it is possible to control the molecular weight of the polymer and the number of terminal groups in the polymer chain.
  • Double metal cyanide catalysts are generally prepared by reacting a metal salt, such as zinc chloride, with an alkali metal hexacyanometallate, such as potassium hexacyanocobaltate, in aqueous solution.
  • a metal salt such as zinc chloride
  • an alkali metal hexacyanometallate such as potassium hexacyanocobaltate
  • the resulting double metal cyanide complexes are heterogeneous catalysts.
  • a single crystal X-ray diffraction analysis of Zn 3 [Co(CN) 6 ] 2 ⁇ 12 H 2 O shows that this complex is a three-dimensional coordination polymer comprising bivalent zinc atoms which are linked with cobalt atoms via cyanide bridges. The spaces between the metal atoms are too small that monomers like alkylene oxides and CO 2 could penetrate into the crystal.
  • DMC catalysts are heterogeneous catalysts and small catalyst particles having a high surface-to-volume ratio are believed to have an advantage effect on the catalyst activity. If the particle dimensions are reduced to the nanometer scale, there is another benefit: nanoparticles scatter visible light to a very small degree only. Consequently, despite of catalyst residues the polymerization products are substantially less opacified compared to polymerization products obtained by micrometer-scale or millimeter-scale catalyst particles.
  • the synthesis of nanoscopic double metal cyanides is for example described in Polymer 2011, 52, page 5494 . However, the particles described in this reference are in the form of nano-lamelae, i.e. nanoscopic with respect to one dimension only.
  • DMC catalysts generally require activation times of several minutes or even more than one hour which has a negative impact on the polymerization time cycles.
  • the activation time is also referred to as "induction period" to denote the initial period of time of a polymerization reaction during which the catalyst does not show any substantial or a substantially reduced catalytic activity. After the induction period, the polymerization reaction accelerates.
  • induction periods obtained with DMC catalysts may inter alia depend on the way of catalyst preparation and on the contents of water and other impurities present in the catalyst. In other words, a DMC catalyst is not catalytically active immediately after contacting it with alkylene oxides or other monomers. The polymerization starts only after the induction period.
  • the installation of new production capacities requires high development expenses and safety efforts.
  • the polydispersity i.e. the ratio of the weight average molecular weight to the number average molecular weight, can be increased by occurrence of an induction period, which is undesirable for most applications.
  • WO 98/52689 describes a process for shortening the induction period of DMC catalysts by removing water residues via co-evaporation with organic solvents or via introduction of inert gases.
  • WO 01/10933 describes the shortening of the induction period of DMC catalysts by continuous dosing of the alkylene oxide monomer to a concentrated mixture of DMC catalyst and starter substance.
  • WO 03/066706 teaches the shortening of the induction period by introducing alkylene oxide to a mixture of DMC catalyst and starter substance at an internal reactor pressure of less than 1 bar.
  • WO 2013/010987 describes the activation of DMC catalysts for the manufacture of polyether carbonate diols in the presence of heterocumulenes, such as isocyanates, as so-called promoting agents.
  • heterocumulenes such as isocyanates
  • isocyanates are in general very toxic so that a complete conversion or removal of the isocyanates has to be provided for in order to make the produced material available for later use.
  • WO 2012/156431 discloses a DMC catalyst which is said to show a reduced induction period if a polyether polyol triol is added as polymerization initiator and severely dried before charging the catalyst and the monomers to the polymerization reactor.
  • a polyether polyol triol is added as polymerization initiator and severely dried before charging the catalyst and the monomers to the polymerization reactor.
  • very dry polymerization initiator the induction period and, therefore, the problems associated therewith have not been completely avoided.
  • the catalyst should have a high activity which allows the manufacture of polymer products with a low content of catalyst residues.
  • the present invention relates to a process for preparing a double metal cyanide (DMC) catalyst of Formula I M a [M' (CN) c Z w ] b ⁇ zA (I), wherein M is a main group or transition metal cation, M' is a main group or transition metal cation, which can be the same or different from M, Z is an anion or ligand other than cyanide and is preferably selected from the group consisting of chloride, bromide, iodide, azide, alcoholate, carbonyl, carboxylate, cyanate, hydroxide, isocyanate, nitrosyl, nitrate, thiocyanate and water, A is an amphiphilic agent selected from heteroatom-containing organic compounds having at least one polar head group and an aliphatic, aromatic or partially moiety having a number of 6 to 42 carbon atoms, w is an integer greater than or equal to 0, but lower than c, a, b and c
  • the present invention is directed to a DMC catalyst obtained according to the process of the first aspect.
  • the invention is in a third aspect directed to the use of the DCM catalyst of the second aspect in polymerization reactions.
  • step (a) the process of the invention comprises the synthesis of a DMC amphiphile adduct M a [M' (CN) c Z z ] b ⁇ xA ⁇ yL (IV).
  • This step is generally performed by reacting a metal salt M e X f (II) with a cyanometallate complex D g [M' b (CN) c Z w ] (III) in the presence of an amphiphilic agent A.
  • the metal salt used in step (a) is a compound of Formula II M e X f (II), wherein M is a main group or transition metal cation, X is an anion, and e and f are integers greater than or equal to 1 so that metal salt II is electrically neutral.
  • cation M is selected from the group consisting of Ag(I), Al(III), Ce(III), Ce(IV), Cd(II), Co(II), Co (III), Cr(II), Cr(III), Cu(II), Eu(III), Fe(II), Fe(III), La (III), Mg (II), Mn(II), Mo(IV), Mo (VI), Ni(II), Pb(II), Rh(II), Ru(II), Ru(III), Sn(II), Sn(IV), Sr(II), Ti(III), Ti(IV), V(V) V(IV), W(IV), W(VI), Zn(II) and mixtures thereof.
  • cation M is Zn(II).
  • anion X is selected from the group consisting of acetate, acetylacetonate, carboxylate, carbonate, cyanate, cyanide, dihydrogen phosphate, halide, such as chloride, bromide and iodide, hexafluorophosphate, hydroxide, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, isocyanate, isothiocyanate, nitrate, nitrite, oxalate, perchlorate, phosphate, sulfate, tetrafluoroborate, tetrakis(4-biphenylyl)borate tetrakis(4-tert-butylphenyl)borate, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]borate tetrakis[3,5-bis(trifluoro-methyl
  • X is selected from the group consisting of nitrate, chloride, bromide, iodide, acetate, benzoate, acetylacetonate, sulfate and combinations thereof.
  • anion X is nitrate.
  • the metal salt II is preferably selected from the group consisting of zinc(II) nitrate, zinc(II) chloride, zinc(II) bromide, zinc(II) iodide, zinc(II) acetate, zinc(II) acetylacetonate, zinc(II) benzoate, iron(II) sulfate, iron(II) bromide, iron(II) chloride, iron(III) chloride, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) chloride, and nickel(II) nitrate and mixtures thereof. It is particularly preferred that the metal salt II is zinc(II) nitrate.
  • the metal salt II can also be in the form of a solvate.
  • suitable solvate forms include hydrates and solvates with organic solvents and combinations thereof.
  • Preferred examples of suitable solvates include hydrates.
  • zinc(II) nitrate is preferably used in the form of a hydrate, like a hexahydrate.
  • the cyanometallate complex used in step (a) is a compound of Formula III D g [M' (CN) c Z w ] b (III) wherein D is a cation, M' is a main group or transition metal cation, Z is an anion or ligand other than cyanide, such as chloride, bromide, iodide, azide, alcoholate, carbonyl, carboxylate, cyanate, hydroxide, isocyanate, nitrosyl, nitrate, thiocyanate and water, w is an integer greater than or equal to 0, but lower than c, and g, b and c are integers greater than or equal to 1 so that complex III is electrically neutral.
  • D is a cation
  • M' is a main group or transition metal cation
  • Z is an anion or ligand other than cyanide, such as chloride, bromide, iodide, azide, alcoholate, carbonyl, carboxylate
  • suitable cations D include alkali metal ions, such as Li(I), Na(I) and K(I), earth alkali metal ions, such as Mg(II) and Ca(II), non-metallic cations, such as a proton, ammonium, imidazolium and alkylammounium, and mixtures thereof.
  • D is an alkali metal ion like potassium(I).
  • cation M' is selected from the group consisting of Co(II), Co(III), Cr(II), Cr(III), Fe(II), Fe(III), Ir(III), Mn(II), Mn(III), Ni(II), Rh(III), Ru(II), V(IV), V(V) and mixtures thereof.
  • suitable examples of the cyanometallate anion include hexacyanocobaltate and hexacyanoferrate.
  • w is 0 so that anion or ligand Z is absent.
  • the compound of Formula III is selected from the group consisting of potassium hexacyanocobaltate, potassium hexacyanoferrate and mixtures thereof.
  • the cyanometallate complex III can also be in the form of a solvate.
  • suitable solvate forms include hydrates, solvates with organic solvents and combinations thereof.
  • Preferred examples of suitable solvates include hydrates.
  • step (a) is performed in the presence of an amphiphilic agent A which is a heteroatom-containing organic compound having at least one polar head group and an aliphatic, aromatic or partially aromatic moiety having 6 to 42 carbon atoms, preferably 16 to 20 carbon atoms, or in the presence of a salt of the amphiphilic agent A.
  • the amphiphilic agent A is a heteroatom-containing organic compound having at least one polar head group and an aliphatic moiety having a chain length of 6 to 42 carbon atoms, preferably 16 to 20 carbon atoms.
  • the at least one polar head group of amphiphilic agent A is selected from the group consisting of alcohol, amine, thiol, phosphane, and carboxylic groups.
  • the amphiphilic agent A is a primary, secondary or tertiary aliphatic alcohol, amine, thiol, carboxylic acid and/or phosphane.
  • the amphiphilic agent A is a primary aliphatic unbranched amine or carboxylic acid, in particular a primary aliphatic unbranched amine or a primary aliphatic carboxylic acid having 16 to 20 carbon atoms or a salt thereof.
  • amphiphilic agent A can be saturated or partially unsaturated.
  • the amphiphilic agent A is selected from the group consisting of n-hexadecylamine, n-octadecylamine, n-eicosylamine, oleylamine, octadecatrien-1-amine, such as 9,12,15-octadecatrien-1-amine, and combinations thereof.
  • the reaction mixture of step (a) further comprises a solvent L.
  • solvent L include water, alcohols, such as aliphatic alcohols having 1 to 6 carbon atoms like ethanol, methanol, n-propanol, and iso-propanol, ethers, esters, ketones, aldehydes, alkanes, halogenated hydrocarbons, aromatics, sulfoxides, amides, amines, ionic liquids and mixtures thereof.
  • solvent L is a mixture of water and alcohol and in particular a mixture of water and ethanol.
  • the volume ratio of ethanol to water in said mixture ranges from 1:100 to 100:1, more preferably from 1:15 to 9:1, like 1:9 to 5:1 or 1:9 to 4:1.
  • the volume ratio of ethanol to water in the reaction mixture of step (a) ranges from 1:9 to 3:1. It has been found that above volume ratios result in DMC catalysts showing a particularly advantageous polymerization performance.
  • step (a) takes place in pure amphiphilic agent A, such as an amphiphilic agent A which is liquid at room temperature or liquid at the reaction temperature in step (a).
  • amphiphilic agent A can be added to the reactor in a pure form or in the form of a solution or dispersion in a solvent which can be the same or different from solvent L described above.
  • amphiphilic agent A can be added to the reactor in form of a dispersion in water or an alcohol or a water alcohol mixture.
  • A is added to the reactor in form of a dispersion in ethanol.
  • the amount of amphiphilic agent A used in step (a) should preferably correlate to the amount of metal M of metal salt II.
  • the molar ratio of the number of hydrophilic groups of the amphiphilic agent A to the number of metal M ranges from 1:100 to 100:1 and preferably from 2:1 to 4:1 and more preferably is about 2:1.
  • a molar ratio of less than 2:1 may result in that formation of the desired DMC adduct IV is incomplete.
  • the molar ratio of amphiphilic agent A to metal M preferably ranges from 1:100 to 100:1 like from 2:1 to 4.1 and more preferably is about 2:1.
  • the molar ratio of metal M to metal M' preferably ranges from 1:100 to 100:1, more preferably from 1:4 to 4:1 and most preferably is about 20:19.
  • a solution or dispersion of the amphiphilic agent A in solvent L is provided.
  • metal salt II is added to this solution or dispersion in order to obtain a homogeneous mixture of metal salt II and amphiphilic agent A.
  • the cyanometallate complex III is added to this mixture and the resulting reaction mixture is stirred for a certain time to allow the DMC amphiphile adduct IV to precipitate.
  • step (a) is preferably ranging from -20 to 400 °C, more preferably from 0 to 80°C.
  • step (a) is performed at about room temperature.
  • step (a) it is preferred to separate the precipitated DMC amphiphile adduct IV from the reaction mixture.
  • Such a separation can be effected by conventional techniques, such as filtration, centrifugation, sedimentation etc.
  • the isolated DMC amphiphile adduct IV can then be washed.
  • the washing step is carried out to remove impurities from the adduct that will render the final DMC catalyst less active if they are not removed.
  • the adduct IV is washed with the same solvent or solvent mixture L as used in the reaction of step (a).
  • the adduct IV After the adduct IV has been washed, it can be gently dried, such as at a temperature of about 50°C and under reduced pressure, to obtain a dry DMC amphiphile adduct IV. Drying at more severe conditions, such as at higher temperatures, may lead to a removal of the amphiphilic agent A from the adduct, as will be explained below.
  • the adduct IV can be crystalline, partially crystalline or amorphous. Crystalline or partially crystalline adducts are preferred.
  • DMC amphiphile adduct IV obtained at the end of step (a) does typically not show any substantial catalytic activity in the polymerization of alkylene oxides.
  • the adduct IV is thermally treated to yield the catalytically active DMC catalyst I.
  • This thermal treatment is preferably performed by heating the adduct IV, in particular under vacuum, at a temperature of 100 to 400°C, such as 120 to 140°C.
  • the adduct IV is dried, in particular under vacuum, at a temperature of 100 to 400°C, such as 120 to 140°C, until the resulting catalyst I reaches a constant weight.
  • the thermal treatment in step (b) results in that at least a part of the amphiphilic agent A and optionally the solvent L is removed from the adduct IV.
  • the thermal treatment does not only involve the partial removal of amphiphilic agent A, but also results in a reorganization of the catalyst structure and especially of the catalyst surface structure.
  • the surface of the resulting catalyst particles is functionalized with amphiphilic agent A, such as amines, which is in accordance with the incomplete removal of amphiphilic agent A from adduct IV.
  • the adduct IV which per se shows no or only low catalytically activity, serves as a precursor which can be transformed to the active DMC catalyst I.
  • the adduct IV or catalyst I is crushed or milled, e.g. in a ball mill, to facilitate removal of amphiphilic agent by evaporation and to further reduce the particle size of the resulting catalyst.
  • the DMC catalyst I prepared by the process according to the invention via the DMC adduct IV shows a remarkably high catalytic activity useful for alkylene oxide polymerization and does in particular not require long activation times. In fact, no induction period at all occurs when using DMC catalyst according to the invention.
  • the invention provides in a second aspect a DMC catalyst I obtainable by the process of the invention, i.e. M a [M' (CN) c Z w ] b ⁇ zA (I) and a DMC adduct of Formula (IV) M a [M' (CN) c ] b ⁇ xA ⁇ yL (IV) which can be used for the preparation of catalyst I.
  • M, M', Z, A, L, a, b, c, z, x and y are defined as mentioned above in connection with the first aspect of the invention.
  • the metal cation M is a divalent cation, such as Zn(II)
  • integer a is preferably 3 and number x is preferably about 6.
  • the ratio of integer a to number x is preferably about 1:2.
  • integer a is 3 and number z is about 2 to 3. Accordingly, the ratio of integer a to number z in the final catalyst I is preferably ranging from about 1:1 to 1.5:1.
  • Elemental analysis of catalysts I and/or adduct IV shows that small amounts of salts may be associated with the catalyst I and/or the adduct IV.
  • adduct IV and consequently catalyst I can comprise small amounts of KNO 3 .
  • adduct IV and catalyst I are free from such salts.
  • the invention relates to the use of the catalyst in polymerization reactions.
  • the DMC catalyst according to the invention is preferably used as a catalyst in the hompolymerization of an alkylene oxide, such as propylene oxide, or a copolymerization or terpolymerization of two or three monomers selected from alkylene oxides, CO 2 , cyclic carboxylic acid anhydrides, cyclic carboxylic acid esters and cyclic carboxylic acid amides.
  • an alkylene oxide such as propylene oxide
  • a copolymerization or terpolymerization of two or three monomers selected from alkylene oxides, CO 2 , cyclic carboxylic acid anhydrides, cyclic carboxylic acid esters and cyclic carboxylic acid amides such as propylene oxide
  • the present invention also relates to the polymers obtained by using the DMC catalyst in polymerization reactions.
  • the resulting mixture was stirred at room temperature for 18 hours. Then the obtained solid was separated by centrifugation at 25,000 m/s 2 , washed three times with a mixture of ethanol and water and was centrifuged again. Finally, the colorless solid was dried under a dynamic vacuum at 50°C for 24 hours.
  • Catalysts 2 to 4 were obtained in accordance with the method of Example 1. Solely the volume ratio of the mixture of ethanol and water used in the preparation of the DMC octadecylamine adduct was varied. The volume ratio of the ethanol water mixture used for washing the crude reaction product was the same as the volume ratio used in the synthesis step. The amount of octadecylamine was the same as in Example 1.
  • Table 1 shows the EtOH/H 2 O volume ratio used for the synthesis of the DMC amphiphile adducts, their elemental composition and the molecular formula derived therefrom.
  • Table 2 shows the elemental composition of the catalysts obtained from the amphiphile adducts as well as the polymer yields obtained in copolymerization of CO 2 and propylene oxide and the catalyst activity calculated therefrom.
  • Table 1 EtOH/H 2 O volume ratio used for the synthesis of the DMC amphiphile adducts 2 to 4 and 1 (Examples 2 to 4 and 1), their elemental composition and the molecular formula derived therefrom Adduct No.
  • the catalyst 1 can also be prepared in a larger scale.
  • 178 g (0.660 mol) of octadecylamine were dispersed in 0.5 L of ethanol in a glass reactor (10 L) equipped with an overhead stirrer.
  • 4.5 L of water were added to form a mixture of ethanol and water having a volume ratio of 1:9.
  • 89.0 g (0.300 mol) of zinc nitrate hexahydrate were added to the viscous ethanol-water mixture.
  • 63.0 g (0.190 mol) of potassium hexacyanocobaltate were added to this dispersion.
  • the resulting mixture was stirred at room temperature for 20 hours. Then, the obtained solid was separated by filtration over a Büchner funnel, washed three times with a mixture of ethanol and water and separated again. Finally, the colorless solid was dried under a dynamic vacuum at 50 °C for 48 hours.
  • the DMC octadecylamine adduct (230.0 g) obtained thereby was crushed with a glass rod and heated under vacuum to 130 °C. Intermittently the residue was crushed again with a glass rod. Then, octadecylamine was evaporated and therefore removed from the synthesis residue.
  • a DMC catalyst was prepared according to Example 1 of WO 2004/000913 .
  • the obtained filter cake was dried according to the same drying procedure as applied in Examples 1 to 4, i.e. 5.0 g of a DMC filter cake were heated under vacuum to 130 °C for 40 hours. 2.6 g of a colorless solid were obtained.
  • the obtained catalyst is a standard catalyst used in industry.
  • Example 6 Copolymerization of CO 2 and propylene oxide
  • Table 2 shows the polymer yield and the corresponding turnover frequency obtained with Catalysts 1 to 4.
  • Table 3 shows the carbonate content, molar mass, polymer yield and polydispersity obtained with Catalysts 1 and 8.
  • Table 3 Catalytic performance in the copolymerization of CO 2 and propylene oxide with Catalysts 1 (Example 1) and 8 (Comparative Example 1) Run Catalyst No. Polymer yield [g] Induction period [min] Carbonate content [mol-%] M n [kg/mol] Polydispersity 1 1 43.2 0 70 45.7 2.8 2 8 55.1 150 40 16.7 8.5
  • Figure 2 shows the temperature of the polymerization reaction as a function of the reaction time in Runs 1 and 2. Moreover,
  • Figure 3 shows the CO 2 uptake, which is an indicator for the copolymerization rate, as a function of the reaction time in Runs 1 and 2.
  • the reaction temperature was about 60°C throughout the entire polymerization reaction.
  • Catalyst 8 prepared according to Comparative Example 1 shows a different behavior. Using this catalyst the reactor temperature was constant at 60°C up to a reaction time of 150 minutes. During this time the CO 2 up-take rate was somewhat lower than that of Catalyst 1. However, after 150 min a temperature peak occurred when using Catalyst 8, i.e. the reactor temperature suddenly increased from 60 to 140°C. Thus, Catalyst 8 arrived at its maximum activity only about 150 minutes after start of the reaction and the induction period was more than 2 hours.
  • the polymer produced with Catalyst 1 was a polyether carbonate having a carbonate content of 70 mol-%, a number average molecular weight (M n ) of 46 kg ⁇ mol -1 and a polydispersity of 2.8.
  • the polymer produced with Catalyst 8 was a polyether carbonate having a lower carbonate content of 40 mol-%, a molecular weight M n of 17 kg ⁇ mol -1 and a polydispersity of 8.5.
  • a comparison between the polymer yields shows that both catalysts have a similar activity with respect to the copolymerization of CO 2 and propylene oxide.
  • the number average molecular weight obtained without use of starter compound was 5.5 kg ⁇ mol -1 . This molecular weight was decreased to 4.8 and 2.7 kg ⁇ mol -1 , respectively, by using 27 or 135 mmol/l of polyethylene glycol, respectively.
  • the addition of propylene glycol did not have a negative effect on polymer yield, i.e. catalyst activity.
  • the polymers produced by using Catalyst 1 are clear and less colored compared to polymer products obtained with Catalyst 8 under similar polymerization conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Polyethers (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP15172157.8A 2015-06-15 2015-06-15 Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen Withdrawn EP3106221A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP15172157.8A EP3106221A1 (de) 2015-06-15 2015-06-15 Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen
PCT/EP2016/063714 WO2016202838A1 (en) 2015-06-15 2016-06-15 Process for preparing double metal cyanide catalysts and their use in polymerization reactions
US15/736,727 US20180179334A1 (en) 2015-06-15 2016-06-15 Process for preparing double metal cyanide catalysts and their use in polymerization reactions
EP16732991.1A EP3307432A1 (de) 2015-06-15 2016-06-15 Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP15172157.8A EP3106221A1 (de) 2015-06-15 2015-06-15 Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen

Publications (1)

Publication Number Publication Date
EP3106221A1 true EP3106221A1 (de) 2016-12-21

Family

ID=53488150

Family Applications (2)

Application Number Title Priority Date Filing Date
EP15172157.8A Withdrawn EP3106221A1 (de) 2015-06-15 2015-06-15 Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen
EP16732991.1A Withdrawn EP3307432A1 (de) 2015-06-15 2016-06-15 Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP16732991.1A Withdrawn EP3307432A1 (de) 2015-06-15 2016-06-15 Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen

Country Status (3)

Country Link
US (1) US20180179334A1 (de)
EP (2) EP3106221A1 (de)
WO (1) WO2016202838A1 (de)

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500704A (en) 1983-08-15 1985-02-19 The Dow Chemical Company Carbon dioxide oxirane copolymers prepared using double metal cyanide complexes
WO1998052689A1 (en) 1997-05-16 1998-11-26 Arco Chemical Technology, L.P. Process for rapid activation of double metal cyanide catalysts
WO2001010933A1 (de) 1999-08-06 2001-02-15 Bayer Aktiengesellschaft Verfahren zur herstellung von polyetherpolyolen
US20020006864A1 (en) * 1999-06-02 2002-01-17 Georg Heinrich Grosch Suspension of multimetal cyandie compounds, their preparation and their use
WO2003066706A1 (de) 2002-02-07 2003-08-14 Basf Aktiengesellschaft Verfahren zur aktivierung von doppelmetallcyanid-verbindungen
US6608231B1 (en) * 1998-09-16 2003-08-19 Bayer Aktiengesellschaft Double-metal cyanide catalysts for producing polyether polyols
WO2003106025A1 (en) * 2002-06-14 2003-12-24 Shell Internationale Research Maatschappij B.V. Preparation of a double metal cyanide catalyst
WO2004000913A1 (de) 2002-06-24 2003-12-31 Basf Aktiengesellschaft Dmc-katalysatoren, polyetheralkohole sowie verfahren zu deren herstellung
US6878661B1 (en) * 1998-07-31 2005-04-12 Bsyer Aktiengesellschaft Bimetallic-cyanide catalysts used for preparing polyether polyols
US20050181967A1 (en) * 2002-04-26 2005-08-18 Alfred Ruland C<sb>10</sb>-alkanolalkoxylates and the use thereof
WO2012136657A1 (de) 2011-04-04 2012-10-11 Henkel Ag & Co. Kgaa Verfahren zur copolymerisation von epoxiden mit kohlendioxid
WO2012156431A1 (en) 2011-05-17 2012-11-22 Repsol, S.A. Process for preparing highly active double metal cyanide catalysts and their use in the synthesis of polyether polyols
WO2013010987A1 (de) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Verfahren zur aktivierung von doppelmetallcyanidkatalysatoren zur herstellung von polyethercarbonatpolyolen
WO2013011015A1 (de) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Verfahren zur herstellung von polyetherpolyolen
WO2013010986A1 (de) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Verfahren zur herstellung von polyethercarbonatpolyolen
WO2013087582A2 (de) 2011-12-16 2013-06-20 Bayer Intellectual Property Gmbh Verfahren zur herstellung von polyetherestercarbonatpolyolen
EP2837648A1 (de) * 2013-08-12 2015-02-18 Repsol, S.A. Verfahren zur Herstellung von Polyethercarbonatpolyolen

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500704A (en) 1983-08-15 1985-02-19 The Dow Chemical Company Carbon dioxide oxirane copolymers prepared using double metal cyanide complexes
WO1998052689A1 (en) 1997-05-16 1998-11-26 Arco Chemical Technology, L.P. Process for rapid activation of double metal cyanide catalysts
US6878661B1 (en) * 1998-07-31 2005-04-12 Bsyer Aktiengesellschaft Bimetallic-cyanide catalysts used for preparing polyether polyols
US6608231B1 (en) * 1998-09-16 2003-08-19 Bayer Aktiengesellschaft Double-metal cyanide catalysts for producing polyether polyols
US20020006864A1 (en) * 1999-06-02 2002-01-17 Georg Heinrich Grosch Suspension of multimetal cyandie compounds, their preparation and their use
WO2001010933A1 (de) 1999-08-06 2001-02-15 Bayer Aktiengesellschaft Verfahren zur herstellung von polyetherpolyolen
WO2003066706A1 (de) 2002-02-07 2003-08-14 Basf Aktiengesellschaft Verfahren zur aktivierung von doppelmetallcyanid-verbindungen
US20050181967A1 (en) * 2002-04-26 2005-08-18 Alfred Ruland C<sb>10</sb>-alkanolalkoxylates and the use thereof
WO2003106025A1 (en) * 2002-06-14 2003-12-24 Shell Internationale Research Maatschappij B.V. Preparation of a double metal cyanide catalyst
WO2004000913A1 (de) 2002-06-24 2003-12-31 Basf Aktiengesellschaft Dmc-katalysatoren, polyetheralkohole sowie verfahren zu deren herstellung
WO2012136657A1 (de) 2011-04-04 2012-10-11 Henkel Ag & Co. Kgaa Verfahren zur copolymerisation von epoxiden mit kohlendioxid
WO2012136658A1 (de) 2011-04-04 2012-10-11 Henkel Ag & Co. Kgaa Katalysator zur epoxidpolymerisation und zur copolymerisation von epoxid mit kohlendioxid
WO2012156431A1 (en) 2011-05-17 2012-11-22 Repsol, S.A. Process for preparing highly active double metal cyanide catalysts and their use in the synthesis of polyether polyols
WO2013010987A1 (de) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Verfahren zur aktivierung von doppelmetallcyanidkatalysatoren zur herstellung von polyethercarbonatpolyolen
WO2013011015A1 (de) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Verfahren zur herstellung von polyetherpolyolen
WO2013010986A1 (de) 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Verfahren zur herstellung von polyethercarbonatpolyolen
WO2013087582A2 (de) 2011-12-16 2013-06-20 Bayer Intellectual Property Gmbh Verfahren zur herstellung von polyetherestercarbonatpolyolen
EP2837648A1 (de) * 2013-08-12 2015-02-18 Repsol, S.A. Verfahren zur Herstellung von Polyethercarbonatpolyolen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
POLYMER, vol. 52, 2011, pages 5494

Also Published As

Publication number Publication date
WO2016202838A1 (en) 2016-12-22
US20180179334A1 (en) 2018-06-28
EP3307432A1 (de) 2018-04-18

Similar Documents

Publication Publication Date Title
KR100429297B1 (ko) 고활성의이중금속시안화물착체촉매
JP4043061B2 (ja) 改良されたポリエーテル含有二重金属シアン化物触媒並びにその製法および用途
JP4122064B2 (ja) 官能化ポリマーを含有する二重金属シアン化物触媒
EP2709757B1 (de) Verfahren zur herstellung von hochaktiven doppelmetall-cyanidkatalysatoren und deren verwendung in der synthese von polyetherpolyolen
JP3369769B2 (ja) ポリウレタンフォームで支持された２金属シアン化物触媒およびその製造方法、ならびにエポキシドポリマーの製造方法
US8119825B2 (en) Method for the production of multimetal cyanide compounds
US20060276590A1 (en) Method for preparing metal cyanide catalyst complexes using partially miscible complexing agents
JPH07196778A (ja) 二金属シアン化物錯体触媒及びその製造方法ならびに前記触媒を用いてエポキシドポリマーを製造する方法
EP1866084A2 (de) Verfahren zur herstellung von dmc-katalysatoren
EP1409567B1 (de) Doppelmetallcyanidkomplexkatalysatoren
MXPA03001009A (es) Proceso mejorado para la copolimerizacion de oxidos de alquileno y dioxido de carbono utilizando suspensiones de compuestos de cianuro mutimetalico.
JPH1149792A (ja) 亜鉛／金属ヘキサシアノコバルテート錯化合物、その製造方法、およびポリエーテルポリオール製造へのその使用
KR20020081371A (ko) 다금속 시아나이드 화합물의 제조 방법
US6764978B2 (en) Multimetal cyanide compounds
KR101466803B1 (ko) 이중금속시안염 촉매 및 이를 제조하는 방법
JP2006077248A (ja) 複金属シアン化物（ｄｍｃ）触媒の製造方法
TWI717562B (zh) 高活性雙金屬氰化物觸媒及其製備方法與應用
US20050203274A1 (en) Dmc catalysts, polyether alcohols, and method for the production thereof
EP3106221A1 (de) Verfahren zur herstellung von doppelmetallcyanidkatalysatoren und deren verwendung in polymerisierungsreaktionen
KR20120042796A (ko) 새로운 유기 착화물제를 이용하여 합성한 이중금속 시안염 촉매 또는 다중금속 시안염 촉매를 이용한 에폭시계 단량체의 개환 중합에 의한 폴리올 제조
CN102036749A (zh) 用于制备多元醇的具有可控反应性的双金属氰化物催化剂及其制备方法
US6384183B1 (en) Metal hexacyanocobaltate nitroferricyanide complexes
KR20040108674A (ko) 0가 금속을 사용하는 금속 시아나이드 촉매의 제조 방법
KR101129344B1 (ko) 나노 크기 이중금속 혹은 다중금속 시안염 촉매 및 그 제조방법
KR101250954B1 (ko) 에폭시 개환중합반응용 현탁촉매 및 이를 이용한 폴리올의 중합방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20170622